Gas separation by adsorption



June 23, 1953 R. L. HUNTINGTON ETAL 2,642,955

GAS SEPARATION BY ADsoRPTIoN 2 Sheets-Sheet 1 Filed June 25, 1947 `lune 23, 1953 R. L. HUNTINGTON ETAL GAS SEPARATION BY ADSORPTION Filed June 25, 1947 2 Sheets-Sheet 2 SEPEKHTR Laurence .5. Real Patented June 2 3, 1953 GAS SEPARATION BY ADSORPTION Richard L. Huntington and Laurance S. Reid,

Norman, Okla., assignors to Aluminum Company of America, Pittsburgh, Pa., a corporation of Pennsylvania Application June 25, 1947, Serial No. '756,866

(Cl. 18S-114.2)

11 Claims.

This invention is directed primarily to continuous processes for the dehydration of natural gas but is useful in the processing of any gas or iiuid containing adsorbable, liqueable components the separation of which is desired. The processes of the invention are of that type which utilize as adsorbing medium a solid substance such as alumina, silica gel, carbon or similar compound or substance having adsorbing powers, when activated, and r-esponding to reactivation or regeneration to the extent that such powers are at least partially restored when lost,V

in whole or in part, by reason of saturation of the adsorbent with adsorbabl-e substances.

An object of this invention is to provide a continuous process in which a high degree of adsorption efficiency may be obtained at relatively low cost. A further object is to provide continuous gas treating processes operable at high pressures and in which the gas to be treated and the absorptive solids are so handled as to permit use of relatively small amounts of adsorption material and relatively small and efficient adsorption and regenerative v-essels.

Another object is the provision of dehydration processes in which heat losses are maintained at a minimum. A still further object of the invention is the provision of processes of gas treatment which are operable in apparatus having a minimum of moving parts. Other objects of the invention include provision of continuous gas handling methods operable with a minimum consumption of fuel, continuous gas purification methods in which heat balances are largely maintained by manipulation of the gas under treatment, and other and similar objects which will be apparent from the following description of the embodiment of the invention.

The processes embodying the invention will be described with reference to the drawings, in which Fig. 1 depicts in schematic form a npreferred treatment circuit assembled from known devices; and

Fig. 2 shows, in similar fashion, an alternative circuit.

Since the proces-ses of this invention may be practiced without resort to highly specialized mechanism, it being possible and desirable to construct the treatment circuit from known instrumentalities, no details of the various parts of the apparatus are shown.

In carrying out the methods of the invention, any suitable closed adsorbing vessel of suflicient height to insure contact between gas passing therethrough and particles of solid adsorbent disposed therein, may be used. In conjunction therewith is also used a regenerator vessel in which the particles of solid adsorbent are treated to remove such material as may have been adsorbed in the adsorbing vessel and thus restore or reactivate the adsorbent. In the apparatus shown in Figure l the adsorbing vessel l0 is connected to the regenerator vessel H by the pipe l2 in which is disposed a barrel valve i3, or an equivalent valve such as a star valve, which will Ypermit particles of solid adsorbent to be transferred downwardly from the adsorbingzone dened by the vessel I0 to the regenerative zone defined by the vessel H without permitting the simultaneous passage of substantial amounts of gas upwardly from vessel l I to vessel l0. During the dehydration process the movement of the adsorbent particles is substantially continuous in the circuit dened by the adsorbing vessel I0, the pipe l2, the regenerative vessel Il the valve I4 (similar to valve E3 just described), the removal pipe i5, the gas lift It, the separator I1, and the feed pipes I8.

Raw gas to be purified is drawn from a pressured source thereof, the source pressure being such as to insure the unaided travel of the gas throughout the treatment circuit except as later noted. The raw gas enters the system in pipe 20 and the major portion thereof travels through the pressure reducing valve 2l. At a point upstream of said valve 2i a minor portion of the raw gas is diverted from pipe 2B and enters the reactivation or regeneration circuit through pipe f 3B. The major portion of the raw gas, after vpassing pressure reducing valve 2|, enters vpipe 22 through which it flows to the adsorbing zone, entering adsorbing vessel I0 at the bottom of that zone and passing upwardly therethrough. The thus dehydrated gas ilows from the adsorbing zone and then through pipe 23 into condenser 24 where the dehydrated gas is used as a coolant for gas flowing in th-e regeneration circuit, and thence through exit pipe 25 to storage or for use. At a point in the passage of the dehydrated gas from the adsorbing zone to eventual storage or use, a quantity thereof is bled 01T or removed for use in the gas lift I6. In the circuit illustrated this quantity of gas is bled ofi from pipe 25 through pipe 25 and thence to compressor I9 Where the gas is compressed and then fed through pipe 4i] to the gas lift H5. After leaving compressor i9, the compressed gas may, if desired, be passedthrough a gas cooler 4l and expansion nozzle Q2, before owing to the lift device.

The minor portion of raw gas, which is divided from the entering stream of pressure supplied raw gas, travels through pipe 3) to heat exchanger 3| and then through pipe 32 to the heater 33 (which may be of any convenient type) where its temperature is finally raised Y.sufficiently to furnish the needed heat to regenerate the solid adsorbent which is disposed in the regeneration vessel il. From heater 33 the gas ows through pipe 34 into the bottom of the regenerative zone. Thence it passes upwardly through the regenerative vessel il and leaves that vessel at a point near the upper extremity thereof where it flows through pipe 35 and heat `exchanger 3l, where it exchanges a portion of its heat to gas entering the regenerative circuit through pipe Sil. From heat exchanger f3! .the gas now ows through pipe 36 to condenser ,24 where under the cooling-action of dehydrated gas vdelivered to the condenser bypipe h23, the liqueable components, originally adsorbed in the dehydration operation and yielded to the regenerative gas in the regeneration zone, are in large part condensed. The mixture of gas and liquid thus formed by this condensing operation flows `from condenser 24 through pipe 3l' to separator 38 where the liquid phase is separated, collected and drained through the liquid outlet Id3, The gas passing from separator 38 flows through pipe 39, thus leaving the regeneration circuit and being delivered to pipe 22 at a point downstream of pressure valve 2l where it joins the major Yportion of the raw gas as that major portion moves to the adsorbing zone.

During the gas movements just described the particles of solid adsorbent are continuously circulating through their defined path. Entering the adsorbing zone through pipe I8, the adsorbent progresses downwardly through that zone in vessel l0. rThe adsorbent leaves vessel il) through ,j

valve i3 andrpipe I2 and progresses downwardly through the regeneration zone defined by vessel Il, finally passing from vessel Il downwardly through valve ifi and pipe l into the lower part of the gas lift l5 where, meeting the stream of gas from nozzle 42, the adsorbent particles are lifted to a point above the adsorbing zone where they are separated in chamber l1, the adsorbent particles passing through pipe IG into the adsorbing zone, where they again pass through the cycle of movement just described. It will be noted that once the sorbent particles have been delivered at the top of the adsorption zone, their progression downwardly through the adsorbing vessel I0 and then through the regenerator l l is by gravity. Thus throughout the adsorbing process the sorbent particles form a bed of more Aor less continuous mass thus eliminating, to large extent, undesirable suspension of the sorbent particles in the gas under treatment. The lift gas after passing through separator Ii rejoins the stream of processed gas by passing through pipe 43 into pipe 23. It will be noted that this lift gas could be returned to the system by being passed into the top of vessel I0.

As is well known, regeneration of solid adsorbents requires relatively high temperatures, whereas the regenerated adsorbent functions most eiciently at relatively low temperatures, It'is therefore necessary that eiiicient cooling of the regenerated adsorbent take place prior to the time that the regenerated solid adsorbent is contacted by the raw gas which enters the adsorbing zone. It is a feature of the process of this invention that such cooling is effected without .sorbent particles.

'the Vgas lift the use of separate cooling chambers or devices vtion of that. zone are there contacted with processed or treated gas which results from the raw gas contacting adsorbent disposed in the lower portion .of the adsorbing zone. It will be noted in this .connection that the raw gas is fed to the lower portion of the adsorbing zone where it conveniently contacts adsorbent and that thereafter it moves upwardly countercurrent to the progressionof the mass of adsorbent particles downwardly through said zone. Therefore, by the time the rising gas reaches the upper portion of the adsorbing zone and exerts the secondary cooling effect upon the reactivated adsorbent "particles which are entering that zone, the gas vwill have been substantially processed or dehydrated. The cooling thus accomplished is enicient and effective, but yet does not require cooling chambers or physical movement of the adsorbent to an extent greater than that required by the transfer of the regenerated adsorbent from the bottom of the regenerating zone to the lower portion of the adsorbing zone. In the circuit illustrated it will be noted that the amount vof primary cooling effected in the gas lift I5 will vary to some extent with the length of that lift and the period of cont/act between the compressed gas fed from compressor i9 and the ad- Therefore, within limits, the dimensions of the gas lift may be adjusted to obtain the desired cooling effect. However, to avoid bleeding an excessive amount of processed gas'to the compressor I9 to insure complete cool- :part of that zone, thus completing the required cooling in the upper portion of the adsorbing zone prior to the time the downwardly progressing adsorbent particles contact raw, untreated gas. Itis an added advantage of these cooling steps that the coolingris eiected by processed, or substantially processed, gas thereby avoiding material useof the adsorbing power of the adsorbent ipriorito its :contact with raw gas. The cooler 4l and expansion nozzle 42 may be provided, the cooler :to accentuate the cooling eiect and the -nozzle to insure positive lift of the regenerated particles, but these, if desired, may be dispensed withandthe gas'feddirectly to the lift l5 from pipe 40.

With the exception of a limited quantity of dehydrated gas which is compressed for use in l5 as described, all movement throughout the process of gas and adsorbent treatment is caused by the original pressure on the raw gas which enters the system. This .is effectively accomplished by dividing the minor quantity of raw gas which is to be used in the :regeneration of the adsorbent at a point prior to that point Where the pressure of the major raw gas portion is reduced, and by nally feeding the gas from the regeneration circuit into the dehydrating circuit at a low pressure point. It Will also be observed that the compressor I5 and the valves I3 and I4 represent the only moving mechanisms necessary to the practice of the process and that leakage in either of these moving mechanisms will affect but slightly the total pressure relations essential to the flow of the gas through the dehydrating and regenerating circuits. Valve I4 is not necessary but is desirable to insure a steady regulated flow of regenerated particles to the gas stream.

A further advantage of the process of this invention lies in efcient utilization of waste heat carried by the gas owing from the regeneration step'to supply a portion of the heat required by the gas flowing into the regeneration step, the exchange of heat for this purpose like- Wise serving to reduce the temperature of the laden gas moving from the regeneration zone, so that the cooling effect of processed gas flowing from the adsorption zone ,will be usually suiiicient to condense a large part of the liquefiable components of the laden gas, thus allowing ready separation thereof before the gas flows from the regenerative circuit to join the row gas flowing to the adsorbing zone.

The alternate circuit illustrated in Figure 2 has many of the advantages of the circuit just described but is designed for use where the original raW gas pressure is high and where an eiiiuent ofl higher moisture content mayV be tolerated as an end product. The system shown includes an adsorber 50 and regenerator chamber 5I connected by pipe 52 in which is located a barrel valve 53. Sorbent material from the regenerator 5I flows by gravity through barrel valve 54 to the gas lift 55 from which the sorbent passes into separator 55 and thence through rduct 51 into the adsorber 50 (the lift gas being returned to the processed gas circuit through pipe 6I). In every respect the flow and cooling of the particles of "sorbent are as specifically described in connection with the circuit shown in Figure 1. Raw gas is fed into adsorber 55 through intake pipe 58, pressure reducing valve 59 and pipe BIJ. From adsorber 50 the treated gas passes throughlpipeBZ and condenser 53 to outlet pipe 64 from whichit flows to use or storage, all as described with reference to the circuit shown in Fig. 1. To furnish regeneration fluid a vportion of raw gas bled off from inlet pipe 58 through pipe 65 is passed through pressure reducing valve 55, heat exchanger 51, pipe 68, heater 52 and pipe 1l] to the regenerator 5I and thence through pipe 1I. heat exchanger 51, pipe 12, condenser 63, pipe 13, separator 14 and pipe 15 to pipe BI), all in the manner and for the purpose set forth with respect to the equivalent regeneration circuit shown in Fig. 1. In contradistinction to the circuit shown in Fig. l, the gas used in the circuit of Fig. 2 to convey the sorbent particles through the gas lift 55, the chamber 55 and into the adsorber is not taken from the supply of treated gas and thereafter compressed but is, instead, taken from the source of raw gas and, without compression, fed directly into the gas lift 55. Thus a portion of the gas bled from pipe 58 through pipe 55 is diverted, in the circuit shown in Fig. 2, directly into the gas lift 55 through, preferably but not necessarily, expanding nozzle 15.

'I'he advantage of the circuit of Fig. 2 just described lies in the complete elimination of any compressor device thus limiting the moving parts of the circuit solely to the necessary valves. -The disadvantage of the circuit of Fig. 2 lies in the dilution of the treated gas issuing from the adsorber and some contamination of adsorbing particles where at the end of their passage through gas lift 55 their temperature is reduced to such extent as to allow some effective adsorbing action. Otherwise the circuit of Fig. 2 has the advantages above described with reference to the circuit of Fig. 1.

Having thus described our invention, We claim:

1. In a cyclic method for removing an adsorbable component from gas containing the same, the combination of steps comprising dividing raw gas from a pressured source thereof into a major portion and a minor portion, reducing the pressure oi said major portion and then flowing the same into a relatively cool adsorbing zone countercurrent to the progression of a substantially continuous mass of sorbent particles moving through and from said zone toward and into a hotter regenerative zone, passing the major portion of gas from the top of the adsorbing zone as treated gas, removing from the thus treated gas a quantity thereof prior to delivery of the treated gas, compressing said removed quantity, conducting a flow of said compressed quantity to the adsorbing zone, feeding regenerated sorbent particles from said regenerative zone into the flow of said compressed gas to effect delivery of said particles to the adsorbing zone, separating the regenerated particles from the flow of compressed gas, delivering said particles to the adsorbing zone and conductingthe compressed gas into the stream of treated gas, heating the said minor portion of the raw gas, passing said heated minor portion into contact with sorbent particles in the regenerative zone, conducting a flow of all of said minor gas portion out of said regenerative zone, condensing liquei'lable elements from said minor gas portion, separating said liquefiable elements, owing the thus stripped minor gas portion into the adsorbing zone.

2. The process of claim 1 characterized by the fact that at least a portion of the heat applied to the minor portion of the raw gas prior to its entry into said regenerative zone is transferred thereto from gas flowing from saidregenerative zone.

3. The process of claim 1 characterized by the fact that the temperature of the compressed quantity of gas is adjusted to effect cooling of the sorbent particles carried thereby from the regenerative zone to the adsorbing zone.

4. The process of claim 1, characterized by the fact that the compressed quantity of gas is expanded to effect cooling of the sorbent particles carried thereby from the regenerative zone to the adsorbing zone.

5. The process of claim 1 characterized by the fact that the temperature of the compressed quantity of gas is cooled to effect cooling of the sorbent particles carried thereby from the regenerative zone to the adsorbing zone.

6. The process of claim 1 characterized by the fact that the compressed quantity of gas is expanded and cooled to effect cooling of the sorbent particles carried thereby from the regenerative zone to the adsorbing zone.

'1. In a cyclic method for removing an adsorbable component from gas containing the same, the combination or" steps comprising dividing raw 7 gas from a pressured source thereof into a major portion anda minor portion, reducing the `pressure of said major portion and then iiowing the same into a relatively cool adsorbing zone coun- `tercurrent to the progression of a substantially continuous mass of sorbent particles moving through and from said zone toward and into a hotter regenerative zone, passing the major portion of gas from the top of the adsorbing zone `as treated gas, heating the said minor portion of the raw'gas, passing said heated portion into contact with sorbent particles in the regenerative zone, passing all of said heatedminor gas portion out of said regenerative zone, condensing liqueable velements from said minor gas portion, separating said liqueable elements, owing the thus stripped minor gas portion into the adsorbing zone, bleeding a third gas portion from the gas in the system conducting a flow of said third portion under pressure to the adsorbing zone, feeding regenerated sorbent particles from said regenerative zone into the `flow of said third portion to eiect delivery of said particles to the adsorbing zone, and separating the regenerated particles from the flow of gas under pressure delivering said particles to the adsorbing zone and conducting the vgas into the stream of treated gas.

8. In a cyclic method for removing adsorbable component from gas containing the same,v the combination of steps comprising dividing raw gas from a pressured source thereof into a major portion and two minor portions, reducing the pressure of said major portion and then flowing the same into a relatively cool adsorbing zone countercurrent to the progression of a mass of lsorbent particles moving through and from said lzone toward and into a hotter regenerative zone, conducting a flow of one of said minor portions of raw gas toward the adsorbing zone at the top thereof, feeding regenerated sorbent particles from said regenerative zone into the iioW of said minor raw gas portion to effect delivery of said particles to the adsorbent zone, heating the other of said minor portions of raw gas, passing said v i heated raw gas portion into contact with sorbent particles in the regenerative zone and thereafter flowing all of said heated portion from said regenerative zone, condensing liqueable elements from said portion, separating said liqueiiable elements, flowing the thus stripped portion into the adsorbingzone.

9. The process of claim 8 characterized by the 'S fact that a 'portion of the heat applied to the gas portion .flowing into the ,regenerative `zone 1s transferred thereto from gas flowing from said regenerative zone.

10. In a cyclic method for removing adsorbable component from gas containing the same, the combination of steps comprising dividing raw gas from a pressured source thereof into a major portion and a minor portion, reducing the pressure of said major portion and then owing the same into a relatively cool adsorbing zone countercurrent to the progression of a mass of sorbent particles moving through and from said zone toward and into a hotter regenerative zone, heating the minor portion of the raw gas, passing said heated portion into Contact with sorbent particles in the regenerative zone, flowing all of said minor gas portion out of said regenerative zone, condensing liqueable elements from said minor gas portion, separating said liqueable elements, flowing the thus stripped minor gas portion into the adsorbing zone, separating another portion of said raw gas from said pressured source, separately conducting a'ow of said other portion toward the adsorbing zone, feeding regenerated sorbent particles froin said regenerative zone into the flow of said other separated portion to effect delivery of said particles to the adsorbing zone.

11. The process of claim 10 characterized by the fact that a portion of the heat applied to the portion of the raw gas supplied to the regenerative zone prior to its entry into said zone is transferredthereto from gas owing from said regenerative zone.

RICHARD L. HUNTINGTON. LAURANCE S. REID.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 1,422,007 Soddy July 4, 1922 1,577,534 Miller Mar. 23. 1926 1,825,707 Wagner, Jr. Oct. 6, 1931 1,836,301 Bechthold Dec. 15, 1931 1,948,779 Abbott et al. Feb. 27, 1934 2,495,842 Gilliland Jan. 31, 1950 2,507,608 Miller May 16,' 1950 FOREIGN PATENTS Number Country Date 317,629 Great Britain Aug. 22, 1929 

7. IN A CYCLIC METHOD FOR REMOVING AN ADSORBABLE COMPONENT FROM GAS CONTAINING THE SAME, THE COMBINATION OF STEPS COMPRISING DIVIDING RAW GAS FROM A PRESSURED SOURCE THEREOF INTO A MAJOR PORTION AND A MINOR PORTION, REDUCING THE PRESSURE OF SAID MAJOR PORTION AND THEN FLOWING THE SAME INTO A RELATIVELY COOL ADSORBING ZONE COUNTERCURRENT TO THE PREGRESSION OF A SUBSTANTIALLY CONTINUOUS MASS OF SORBENT PARTICLES MOVING THROUGH AND FROM SAID ZONE TOWARD AND INTO A HOTTER REGENERATIVE ZONE, PASSING THE MAJOR PORTION OF GAS FROM THE TOP OF ADSORBING ZONE AS TREATED GAS, HEATING THE SAID MINOR PORTION OF THE RAW GAS, PASSING SAID HEATED PORTION INTO CONTACT WITH SORBENT PARTICLES IN THE REGENERATIVE ZONE, PASSING ALL OF SAID HEATED MINOR GAS POR- 